First VC Material

CHE2612
VC 27/07/2019
First VC Material (27/07/2019)
Specific Outcome 1: Describe properties of pure gases
ALL mentioned equations and figures not in this document are in the prescribed textbook.
In Figure 4A.4 (prescribed textbook, PT) is what we call a pressure–temperature phase
diagram. A phase diagram shows regions of thermodynamic phase stability of a substance,
meaning the substance has under the shown conditions no tendency to change into a different
phase. The lines inside the diagram outline the borders between phases. A very large number
of pure chemical substances exist in nature and they can occur in more than the three phases
shown in the diagram, that is, solid, liquid or gas and we know this in the case of water, which
forms many solid states under different conditions as shown in figure 4A.9, PT. We begin,
however, by looking at just the three we commonly encounter and you must learn drawing a
simple phase diagram as shown below.
Fig.1 Water p-T phase diagram

To draw such diagrams we use combinations of the physical properties pressure p, temperature
T, volume V and the values we plot are obtained experimentally. [Note: Under fundamental
constants on front cover, Part 2 Units p 634, and page 6 of PT are symbols for physical
properties and format of units you must adhere to]. Most common are two dimensional phase
diagrams in which only two physical properties are plotted against each other. Any point on
the diagram identifies the physical state in which the substance occurs under the conditions
stated by the values of the plotted physical properties. Take the phase diagram in figure 1
The behaviour of pure gases at high temperatures and low densities gases (p → 0) is well
above: At room temperature (~25 ) and ambient pressure (1 atm) water appears in liquid form
approximated by the ideal gas model. Experiments by Boyle and Charles show ideal behaviour
and we find the corresponding state on the diagram (where a horizontal representing the
that is generalized in figures 1A.2, 1A.3, 1A.4 and 1A.5, PT. These diagrams correspond to
pressure crosses a vertical representing the temperature) in the liquid phase region. In this
equations 1A.3a to 1A.3c, p7 called limiting laws.
specific outcome we concern ourselves with gas behaviour, meaning states to the right of the
curve ACE. Because of the complex behaviour of substances we consider first gases at very
low density and for this purpose we use a p-v phase diagram. See figure 1C.2.
Sketch A
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Sketch B
What do the figures 1A.2, 1A.3, 1A.4 and 1A.5 tell us? You must these figures as scientific
statements or predictions made by the ideal gas model. Figure 1A.2 shows the prediction made
by Boyle’s law in equation 1A.3a that when a fixed amount of ideal gas is held at constant
temperature the product of any pressure and any volume remains constant. Say now you change
the pressure the volume will respond by a change that restores the product value you had before
and the pressure will also respond in the same way to any change in the volume. You can now
make as many changes as will at constant temperature and when you plot your values as shown
in figure 1A.2 you get a curve we call an isotherm. If you now repeat your experiment at
different temperatures you get several isotherms and your plot will look like figure 1A.2.
Sketch B shows other types of plots that give you isotherms. When we now compare the
isotherms predicted by the ideal gas model to real gas isotherms in fig.1 we observe that the
prediction are in agreement but only at high temperatures and high volumes (or low densities).
To answer the question why this is so, we must remember that an ideal gas has no
intermolecular interactions and we conclude therefore that the atoms or molecules in a real gas
at low densities and high temperatures are so far apart that they no longer interact and the real
gas then behaves like an ideal gas.
We can carry out a second experiment to verify Charles’s law by placing a fixed amount of gas
in a container as before but now we ensure that the pressure is constant. We find that under
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these conditions the quotient of volume and temperature (V/T) is a constant and it does not
matter whether we change the volume first or the temperature the quotient will remain constant.
If we now plot from our experiment the values for volume against temperature we get a straight
line called an isobar and after repeating the exercise at different pressures we get a plot as
shown in figure 1A.4. Sketch A shows some isobar plots. You must keep in mind that Charles’s
law is valid only at low densities and as density increases the atoms come closer together and
begin to interact and that ends the validity of ideal gas behaviour. The second part of Charles’s
law involves swapping pressure for volume and carrying out the experiment again. Each
straight line we obtain here is called an isochore, see figure 1A.5.
In conjunction with the limiting laws the Avogadro’s principle in equation 1A.3d allows us to
write a combined expression the ideal gas law, the simplest form of equation of state. An
equation of state is a mathematical function of any of the intensive physical properties p, V, T
in terms of the remaining two. In other words to describe a state of any substance we need only
to know two independent intensive state properties, which allows us to know the corresponding
values of all other intensive properties of the substance. However, if we have as among the
independent variables an extensive property than we must also know the amount of substance
n.
It must be clear by now that the ideal gas law makes exactly the same statements or predictions
as the limiting laws from which it derives. The main differences between ideal and real gas
behaviour occur where application of ideal gas law gets overstretched or goes beyond the
required limits. Condensation occurs when the real gas particles interact and the densities are
therefore higher than satisfies the model. Further, the ideal gas particles are regarded as
massless points, which means they do not occupy space like in the real gas. The departure of
ideal gas model occurs where the isotherms no longer form hyperbolas, the isochores and
isobars no longer form straight lines.
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Next we will look at mathematical functions developed to model real gas behaviour.

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CHE2612

diagram. A phase diagram shows regions of thermodynamic phase stability of a substance,

simple phase diagram as shown below.

Fig.1 Water p-T phase diagram

gas then behaves like an ideal gas.

straight line we obtain here is called an isochore, see figure 1A.5.

equation of state is a mathematical function of any of the intensive physical properties p, V, T

isobars no longer form straight lines.

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